Hydraulic cement composition



Patented Feb. 10, 1948 HYDRAULIC CEMENT COMPOSITION Donald R. MacPherson. University Heights. Ohio, assignor to The Master Builders Company, Cleveland. Ohio. a corporation of Ohio No Drawing. Application October 20, 1945, Serial No. 623.603

8 Claiml. (CL 106-90) This invention relates to hydraulic cement compositions such as concrete or mortar and to indurating compositions for addition to concrete or mortar mixes. It especially relates to such compositions and mixes containing a plasticizing agent which permits substantial improvement in the strength of structures prepared from such com ositions.

The use of agents such for example as waste sulilteiigupr to reduce the water-cement ratio of an hydraulic cement mortar or concrete has permitted substantial im rovement in the properties of structures formed thereof. However, there have been some disadvantages connected w th the use of the agents heretofore proposed which have in some measure limited the commercial acceptance of the cement compositions containing them. Thus. when small amounts of waetasulata iaue 91: the fififl luethereof is added to cement mixes. as disclosed in United States Patents 2.169.980 and 2.229.311 of Edward W. Scr pture. the water-cement ratio may be reduced a very substantial amount and the strength of the concrete at later ages is substantiallv increased. The use of these plasticizing a ents with some cements may be -disadvanta eous in that the strength at early ages. such as one to seven days. may be less than that of the plain mortar or concrete mix. and in that the amount for optimum results in some instances may be critical, even though an accelerator be resent.

It is an ob ect of the present invention to provide a cement composition or an indurating com osition for cement mixes comprising ingredients of low cost which markedly plasticize concrete or mortar mixes, which improve the stren th of the concrete at later ages and which are not deleterious to cement mixes it inadvertently added in relatively larger amounts than usually recommended.

It is another obiect of the present invention to provide im roved strength at early and late a es of a concrete or mortar mix of a given consistencv made with a lower water-cement ratio than that of a plain mortar or concrete mix having the same proportions of cement and aggregate.

It is another ob ect of the present invention to provide a methode of preparing concrete hav- 60 ing imp cgmpressive s trgngt h p it gm well as atlate ages.

A further ob ect of the present invention is to provide an indurating composition for addiremoved.

ates the ratio oi hardening of the een entgswell as'perm'itting a''r?duction iii the water-cement rams"'si ifis tr fi eijsmarfle'streaath- *rstm' ffi'i'tfirbbict 'of the present invention is to providea dry cement which when mixed with aggregate and sand permits a reduction in the normal amount oi water at a given consistency and gives a higher strength to products made therewith.

I have found that the above and other obiects, which will be apparent from the following description of the invention. are accomplished by incorporating in the cement "residuum solids of fermented sulflte liquor. This term designat' solids from the residue of waste sulflte liquo such as has been fermented and from which the r fermented product, such as an alcohol, has bee a I have found that residuum solids of fermented sulfite liquor produce resultant cement mixes that are greatly superior to those produced wit raw waste sulflte liquor or lignin constituen t separated from waste sulfite liquor.

The datta herein reported indicate that the fermentation of waste sulfite liquor or the distillation of the fermented liquor to remove the alcohol therefrom modifies the character of the active constituents normally in the liquor so that the residuum solids so obtained give substantially improved properties to cement mortar or concrete mixes. a

As little as .01% based on the wei ht of the if.

cement. of the residuum solids {engages teli uorisno c a e co ve nimpro ne e 85 proper es of ce e t or co ete ix s and products produced %fiom. in amount of these residuum solids much greater than 5% or .6% by weight of the cement is not usually commercially economical. and for most pur oses smaller 40 amounts of residuum solids of fermented sulflte 'IdesirabTifidmatinz-commsitian jmmnh mixes comprises residuum solids or e ca mg or m n gaQ; liquor. a fine y Y ma a suc as a ozzolana. sum.

1 co an or an agfisu u o accelerate the ra e 0 ar enina and se ng. These ingredients may be proportioned to provide .05% to .6% of the residuum solids of fermented sulfite liquor and if an accelerator is desired. the ingredients are proportioned to protion tocement or concrete mixes which acceler- 55 vide 1% to 2% or 2.5% of the accelerator.

These percentages are based on the weight of the cement. The additional ingredients. such as fig ..ash.,and other finely divided materials, are

L... iiilypresent in admixture with the aforementioned residuum solids in the indurating composition.

Dry, wet or dissolved residuum solids of fermented sulfite liquor are found to give exceptional results when used in cement, mortar or concrete mixes together with a deriv of b zoic egg, such as set forth in one or more of the e States Scripture Patents Nos. 2,264,336, 2,360,517, 2,360,518 and 2.360,519. The preferred derivative of benzoic acid is salicylic acid or a salt thereof.

An especially desirable indurating composition for cement mixes comprises the residuum solids of fermented suifite liquor and a substituted benzoic acid, or a salt or ester thereof, such as salicylic acid, or a compound containing the salicylic group. with or without an acceler tor such as caici r and with or wi't'fiout a finely ed filling material such as ozzo ana. The ingredierits in this indurating composition should be so proportioned that when the composition is mixed with cement there will be present about .05% to about 06% of the residuum solids of fermented sulfite liquor and at the same time 01% to of substituted benzoic acid, salt or ester thereof, The pozzolanic material may be present in any suitable proportion in an indurating composition, but the accelerator, such as calcium chloride, if used should be present in the amount of .1% to about 2.5% by weight of the cement when the indurating compostion is incorporated in the cement, concrete or mortar mix to improve the properties thereof.

Applicant's product can best be defined by the process of manufacture, as the ordinary commercial chemical analysis does not adequately characterize the active ingredients or distinguish these materials over those present in the products roduced by other methods. The improved character of the product of the present invention is primarily noted in the character of the cement compositions in which it is present.

The improvement in properties of concrete containing residuum solids of fermented sulfite liquor (which may if desired be retained in a liquid bag of cement. To mix No. 3 was added the identical amount of lndurating composition, but differing from that of mix No. 2 in that the dried waste sulflte liquor was substituted by the same amount of residuum solids of fermented sulfite liquor. Each of the mixes was prepared with sulficient water to provide approximately the same plasticity, as measured by the slump using a sixinch cone. The concrete of each mix was cast into 2" x 2" cubes. The compressive strength of three cubes from each batch was measured after one day, and the compressive strength of three additional cubes from each batch was measured at the end of twenty-eight days. The pertinent data, including water-cement ratio (W/C) in terms of gallons of water per sack of cement. coment factor (0. F.) of concrete in sacks of cement per cubic yard of concrete, plasticity as measured by the slump and the unit weight of the concrete in pounds per cubic foot, are shown in the following table:

Cosmpregs'sive ren a g (Lila/sq. in.) (P. C. F.)

Slump 1 Day 28 Days Example 2 Three separate concrete mixes were prepared,

each mix comprising 22 pounds of Portland eement, 56 pounds sand and 82 pounds of /4, inch tone. The ilrst'm' ix served as the control. To second mix was incorporated .4% based on the weight of the cement, of the dried residue of waste sulilte liquor. To the third mix was added 4%. based on the weight of the cement, of residuum solids of fermented sulflte liquor. Sufficient water was added in each case to provide a slump of three inches'as measured by a 12 inch cone. Six inch by twelve inch cylinders were used to measure the compressive strength of the concrete at 1, 3, 7 and 28 days. The results are shown in the following table, each value given for compressive strength representing the average value medium) over properties obtained through the for several cylinders.

U it Com IIESSi/VB timgngth w/c or. Slump (0.1.8.) (s. o. v.) (111.) m??? iday 3days Idays ZSdays 1 1.33 am a has ass 2.400 3.290 4,600

2 Me 5.42 a 146.4 so 1.340 2.910 4.600

a we we a 145.2 475 2.510 3.110 5.200

use of equal amounts of other agents heretofore Example 3 proposed may be seen from the following examples in which parts are by weight.

Example 1 Three separate mixtures were prepared. each Four separate mixes were prepared, using the same proportion of cement and aggregate. Each mix, with the exception of the first, which served as the control, contained 500 grams of an hydraulic cement. such as Portland cement, 1375 grams of sand, 1125 grams of pea gravel, and 32% by weight of the cement of 1g agent. The

percentage of plasticizing age s on the amount of solids which would remain as the material was vacuum dried at C. until no further loss in weight occurred. In the preparation '75 of each of the mixes, the water-cement ratio EXAMINE Relative Compressive S h (main mix Mix taken as 100) 7 days 28 days Ann-- Mix No. 1 in the above table is the plain mix. In mix N0. 2 the addition was a concentrated product (syru y liquid) obtained by dialyzing neutralized and concentrated waste sulfite liquor.

In mix No. 3 the addition was a Eurifieg lignin complex com ound obtained in e arm of a HE powder reduced b the Howard rocess,

poun w y e. mix No. 4, the plastic z ng mum solid of fermented suliite liquor.

It will be seen from the above that residuum solids of fermented sulfite liquor provided far greater compressive strength at ages of seven days or more in concrete than was obtained by the use of the other plasticizing agents, all derived from waste sulflte liquor by processes wherein the l gnin complex compound was separated from the balance of the waste liquor.

It will be seen from the above examples that cement compositions containing residuum solids of fermented sulflte liquor are superior in strength. both at early and late ages, to the above cement compositions which do not contain any additions. Referrin to Example the cement compositions containing waste sulfite liquor at one day had materially less strength than the concrete which did not contain anv addition. The concrete containing residuum solids of fermented sulflte li uor had a strength two and onehalf times greater than that without addition. Wh le the strength of the concrete containing waste sulfite liquor at twenty-eight days was substantially greater than that of the concrete which did not contain any addition, the strength of the concrete containing residuum solids of fermented sulflte liquor showed a further large improvement.

From the table of Example 3. it is apparent that the mere purification of the active constituents of waste sulfite liquor does not explain the marked improvement which I have obtained with the residuum solids of fermented sulfite liquor. Thus, comparing mixes No. 2 and No. 4, it is clear that strengths of concrete prepared in accordance with the present invention were far superior, both at early and later ages, to those obtained from concrete prepared by utilizing lignin sulfonates extracted from waste sulfite liquor by a dialysis process. Similarly, comparing mixes No. 3 and No. 4, it is clear that while the active lignin compound used in mix No. 3, which is a lignin compound separated in relatively pure form by a precipitation process, gave improved strength to concrete, it does not give 6 anywhere near the strength obtained with the residuum solids of fermented sulfite liquor.

The Portland cement utilized in the above examples may be substituted by other hydraulic cements, such as aluminous cement. The quantities of the ingredients may be varied or the aggregate may be omitted entirely in accordance with the usual practice as recognized by those skilled in the art.

Furthermore, it is to be understood that the particular form of product shown and described and the particular procedure set forth are presented for purposes of explanation and illustration. and that modifications of said product and procedure can be made without departing from my invention as defined in the appended claims.

What I claim is:

1. A dry cement composition comprising an hydraulic cement and .0l% to .6%. based on the weight oi the cement. of residuum solids of fermented sulflte liquor. said residuum solids being substantially devoid oi fermentable sugars pr sent in the unfermented waste sulfite liquor.

2. A dry cement composition comprising an hydraulic cement. 111% to .6%, based on the weight of the cement. oi residuum solids of fermented sulflte liquor, and .1% to 2.5% of calcium chloride and a pozzolanic material. said residuum solids being substantially devoid of fermentable sugars present in the unfermented waste sulfite liquor.

3. A concrete or mortar mix comprising an hydraulic cement and .(il% to .6%, based on the weight oi the cement. of residuum solids of fermented sulfite li uor. said residuum solids being substantially devoid of ferment-able sugars present in the unfermented waste sulflte liquor.

4. A concrete or mortar mix comprising an hydraulic cement, .01% to 6%. based on the weight of the cement. oi' residuum solids of fermented sulflte liquor and .1% to 2.5%. based on the weight of the cement, of calcium chloride, said residuum solids being substant ally devoid of fermentable sugars present in the uniermented waste sulfite liquor.

5. An indurating composition for hydraulic cement mix s comprising residuum sol ds of fermente dsulfite liquor and calcium chloride. said ingredients being proportioned to give when the induratlng composition is incorporated in the cement .01% to .6%, based on the weight of the cement. of residuum solids of fermented sulilte liquor and .1% to 2.5% of calcium chloride, said residuum solids being substantially d void of iermentahle su ars present in the unfermented waste sulfite liquor.

6. An indurating composition for hydraulic cement mixes comprising residuum solids of fer-- mented sulflte liquor. a member of the group consisting of substituted benzoic acids, salts and esters thereof, said ingredients being proportioned to give when the indurating composition is incorporated with the cement .Ol% to .6%, based on the weight oi the cement, of residuum solids of fermented sulfite liquor, and .005% to .5% of said group member. said residuum solids being substantially devoid of fermentable sugars present in the unfermented waste sulfite liquor.

7. The composition of claim 6 which also contains a pozzolanic material.

8. An indurating composition for hydraulic cement mixes comprising residuum solids of fermented waste sulfite liquor and calcium chloride, saids residuum solids being substantially devoid UNITED STATES PATENTS 7 of fermentable sugars present in the untermented waste sulfite liquor.

Date

130mm R. MACPHERSON. Number Name 2.081.642 Scripture May 27. 1937 REFERENCES CITED 5 2360.519 Scripture Oct. 17. 1944 The following references are of record in the 1,042,538 Ellis Oct. 29, 1912 file of this patent: 

